We report on the synthesis, characterisation, and physical and tribological properties of halogen-free ionic liquids based on various chelated orthoborate anions with different phosphonium cations, both without halogen atoms in their structure. Important physical properties of the ILs including glass transition temperatures, density, viscosity and ionic conductivity were measured and are reported here. All of these new halogen-free orthoborate ionic liquids (hf-BILs) are hydrophobic and hydrolytically stable liquids at room temperature. As lubricants, these hf-BILs exhibit considerably better antiwear and friction reducing properties under boundary lubrication conditions for steel-aluminium contacts as compared with fully formulated (15W-50 grade) engine oil. Being halogen free these hf-BILs offer a more environmentally benign alternative to ILs being currently developed for lubricant applications.

An analysis of a lubricated conformal contact is carried out to study the effect of surface texture on bearing friction and load carrying capacity using computational fluid dynamics. The work focuses on a journal bearing with several dimples. Two- and three-dimensional bearing geometries are considered. The full Navier—Stokes equations are solved under steady-state conditions with a multi-phase flow cavitation model. The coefficient of friction can be reduced if a texture of suitable geometry is introduced. This can be achieved either in the region of maximum hydrodynamic pressure for a bearing with high eccentricity ratio or just downstream of the maximum film for a bearing with low eccentricity ratio. An additional pressure build-up produced as a result of the surface texture has been shown at low eccentricity ratios.

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Results of a numerical study of the influence of micro-patterned surfaces in hydrodynamic lubrication of two parallel walls are reported. Two types of parameterized grooves with the same order of depth as the film thickness are used on one stationary wall. The other wall is smooth and is sliding with a specified tangential velocity. Isothermal incompressible two dimensional full film fluid flow mechanics is solved using a Computational Fluid Dynamics method. It is shown that, by introducing a micro-pattern on one of two parallel walls, a net pressure rise in the fluid domain is achieved. This produces a load carrying capacity on the walls which is mainly contributed by fluid inertia. The load carrying capacity increases with Reynolds number. The load carrying capacity is reported to increase with groove width and depth. However, at a certain depth a vortex appears in the groove and near this value the maximum load carrying capacity is achieved. It is shown that the friction force decreases with deeper and wider grooves. Among all geometries studied, optimum geometry shapes in terms of hydrodynamic performance are reported.

We have developed an all-atomistic force field for a new class of halogen-free chelated orthoborate-phosphonium ionic liquids. The force field is based on an AMBER framework with determination of force field parameters for phosphorus and boron atoms, as well as refinement of several available parameters. The bond and angle force constants were adjusted to fit vibration frequency data derived from both experimental measurements and ab initio calculations. The force field parameters for several dihedral angles were obtained by fitting torsion energy profiles deduced from ab initio calculations. To validate the proposed force field parameters, atomistic simulations were performed for 12 ionic liquids consisting of tetraalkylphosphonium cations and chelated orthoborate anions. The predicted densities for neat ionic liquids and the [P6,6,6,14][BOB] sample, with a water content of approximately 2.3-2.5 wt %, are in excellent agreement with available experimental data. The potential energy components of 12 ionic liquids were discussed in detail. The radial distribution functions and spatial distribution functions were analyzed and visualized to probe the microscopic ionic structures of these ionic liquids. There are mainly four high-probability regions of chelated orthoborate anions distributed around tetraalkylphosphonium cations in the first solvation shell, and such probability distribution functions are strongly influenced by the size of anions.

A flow analysis is carried out for an inclined slider bearing with the aim of showing the governing mechanism at conditions where an optimum in load carrying capacity is achieved. The effects of surface texture on pressure buildup and load carrying capacity are explained for a textured slider bearing geometry. Numerical simulations are performed for laminar, steady, and isothermal flows. The energy transferred to the fluid from the moving wall is converted into pressure in the initial part of the converging contact and into losses in the second part. The convergence ratio can be increased, in order to get the greatest pressure gradient, until the limiting value where flow recirculation begins to occur. The texture appears to achieve its maximum efficiency when its depth is such that the velocity profile is stretched at its maximum extent without incurring incoming recirculating flow. The wall profile shape controlling the velocity profile can be optimized for many hydrodynamic contacts.

Atomistic simulations have been performed to investigate the microscopic structural organization of aqueous solutions of trihexyltetradecylphosphonium bis(oxalato)borate ([P6,6,6,14][BOB]) ionic liquid (IL). The evolution of the microscopic liquid structure and the local ionic organization of IL/water mixtures as a function of the water concentration is visualized and systematically analyzed via radial and spatial distribution functions, coordination numbers, hydrogen bond network, and water clustering analysis. The microscopic liquid structure in neat IL is characterized by a connected apolar network composed of the alkyl chains of [P6,6,6,14] cations and isolated polar domains consisting of the central segments of [P6,6,6,14] cations and [BOB] anions, and the corresponding local ionic environment is described by direct contact ion pairs. In IL/water mixtures with lower water mole fractions, the added water molecules are dispersed and embedded in cavities between neighboring ionic species and the local ionic structure is characterized by solvent-shared ion pairs through cation-water-anion triple complexes. With a gradual increase in the water concentration in IL/water mixtures, the added water molecules tend to aggregate and form small clusters, intermediate chain-like structures, large aggregates, and eventually a water network in water concentrated simulation systems. A further progressive dilution of IL/water mixtures leads to the formation of self-organized micelle-like aggregates characterized by a hydrophobic core and hydrophilic shell consisting of the central polar segments in [P6,6,6,14] cations and [BOB] anions in a highly branched water network. The striking structural evolution of the [P6,6,6,14][BOB] IL/water mixtures is rationalized by the competition between favorable hydrogen bonded interactions and strong electrostatic interactions between the polar segments in ionic species and the dispersion interactions between the hydrophobic alkyl chains in [P6,6,6,14] cations.

Friction coefficients for a pyrrolidinium orthoborate ionic liquid as 3 wt% additive in PEG, neat PEG and 5W40.